CN102701731B - Novel thermosensitive ceramic material used for temperature detector - Google Patents
Novel thermosensitive ceramic material used for temperature detector Download PDFInfo
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- CN102701731B CN102701731B CN201210205102.8A CN201210205102A CN102701731B CN 102701731 B CN102701731 B CN 102701731B CN 201210205102 A CN201210205102 A CN 201210205102A CN 102701731 B CN102701731 B CN 102701731B
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Abstract
The invention discloses a novel thermosensitive ceramic material used for a temperature detector. A general formula of a ceramic powder is PbxSr1-xTiO3+aAl2O3+bSiO2+cPbO, wherein x is equal to 0.10-0.20), a is equal to 0.0002-0.001, b is equal to 0.001-0.006, and c is equal to 0.015-0.075. According to the invention, the traditional solid phase method and sol-gel method are adopted for preparation, the prepared thermosensitive ceramic material has wide temperature test range, good linearity and low cost, variation of temperature can be accurately indicated, and test temperature range can be regulated by changing Pb/Sr ratio; and a manufacturing method is simple in process, high in production efficiency, and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of Novel temperature-sensitive stupalith, the temperature sensitive stupalith especially for-70 ℃ ~ 100 ℃ of scopes, belongs to field of inorganic nonmetallic material.
Background technology
Therefore in recent years, along with the raising gradually of Automation of Manufacturing Process degree, the precision of observing and controlling element and observing and controlling scope are had higher requirement, the development as the novel sensitive material of observing and controlling element has become the problem that Material Field is paid close attention to.The measurement of temperature has extremely important status with being controlled in automatic field, and its observing and controlling element is referred to as temp-sensitive sensor.Temp-sensitive sensor (temperature sensor) is to responsive to temperature, temperature variation is converted to the device of electric quantity change, be to have repeatable and regular a kind of sensor, the electromagnetic parameter that utilizes sensitive element varies with temperature and the feature that changes reaches measurement object.As thermocouple sensor and thermal resistance sensor.
Thermocouple temperature sensor is the instrument that utilizes " thermoelectric effect " making of conductor, and its sensitive element is thermopair.Thermopair is welded by two different conductors or semiconductor one end or hinge joint forms.Thermocouple temperature sensor has the defect of oneself, and its remolding sensitivity is lower, and thermal response is slow, easily be subject to the impact of environmental interference signal, also be easily subject to the impact of prime amplifier temperature drift, be therefore not suitable for measuring small temperature variation, cost compare is high simultaneously.Thermal resistance temperature sensor utilizes conductor or semi-conductive electrical resistance temperature variation and the character that changes is worked, and goes out the change in resistance of thermal resistance, thereby obtain the temperature value corresponding with resistance value with instrument measurement.The resistance of thermal resistance temperature sensor and the relation of temperature are non-linear serious, and prepare material and mostly be metal due to it, and character is more active, and the element of therefore making is easily corroded, easily aging, less stable.
Strontium lead titanate pottery has because of it manufacture that good ferroelectric and dielectric properties are widely used in various electronic devices and components, and conventional preparation method mainly contains sol-gel process, solid reaction process and coprecipitation.Strontium lead titanate pottery has very high specific inductive capacity, but its dielectric constant values is unstable, at Curie temperature place, specific inductive capacity reaches maximal value, when temperature is during higher than Curie temperature, dielectric constant values will decline by Curie-Weiss law along with temperature rises, and not have linear relationship.In document, about the report of strontium lead titanate pottery, concentrate on the research of the character such as ferroelectric, dielectric and PTC effect, the variation relation based on dielectric constant with temperature and in the research aspect thermometric, and adopt Al
2o
3-SiO
2the research that-PbO compounding ingredients carries out doping vario-property to strontium lead titanate pottery has no report.
Summary of the invention
The object of this invention is to provide a kind of material dielectric constant and temperature linearity relation is good, can in wider temperature range, change by indicated temperature, there is good stability, and the adjustable Novel temperature-sensitive stupalith of Range of measuring temp.
It is simple that another object of the present invention is to provide a kind of preparation technology, and production efficiency is high, and be suitable for the preparation method of the above-mentioned Novel temperature-sensitive stupalith of suitability for industrialized production.
Implementation procedure of the present invention is as follows:
General formula Pb
xsr
1-xtiO
3+ aAl
2o
3+ bSiO
2ceramic powder shown in+cPbO, wherein, x=0.10 ~ 0.20, a=0.0002 ~ 0.001, b=0.001 ~ 0.006, c=0.015 ~ 0.075.
The preparation method of above-mentioned ceramic powder, comprises the following steps:
(1) by stoichiometric proportion, butyl titanate and ethyl orthosilicate are dissolved in to glacial acetic acid;
(2) aqueous solution of above-mentioned solution and lead, strontium and aluminum metal salt, stirs and obtains light yellow vitreosol;
(3) colloidal sol is stirred to gel, still aging, in the 70-120 ℃ of dry dry gel powder that obtains;
(4) dry gel powder obtains ceramic powder at 700 ~ 1000 ℃ of calcining 0.5 ~ 2h.
In above-mentioned steps (2), described lead, strontium and aluminum metal salt add with the form of nitrate or acetate.
Above-mentioned ceramic powder, further through granulation, compressing tablet, obtains stupalith for 1 ~ 6 hour at 1100 ~ 1350 ℃ of sintering.
Above-mentioned ceramic powder also can adopt solid phase method preparation, comprises the following steps:
By stoichiometric proportion, take respectively SrCO
3, TiO
2and PbO, take distilled water as medium ball milling post-drying, 800 ~ 900 ℃ of calcinings obtain principal crystalline phase powder, by stoichiometric proportion by principal crystalline phase powder and Al
2o
3, SiO
2add water with PbO and form slurry, ball milling.
The preparation method of ceramic powder of the present invention is not limited to sol-gel process and conventional solid-state method, can also adopt coprecipitation and hydro-thermal method.
Stupalith prepared by the present invention can be used as Temperature Detector, its principle of work is as follows: by the stupalith access circuit-under-test preparing, variation due to ceramic medium material environment temperature, cause the variation of ceramic dielectric constant, thereby according to the size of change in dielectric constant, can directly change the size of measuring temperature variation, reach measure temperature, as the object of sensor.The present invention is specially adapted to the temperature range of-70 ~ 100 ℃, but is not limited in this temperature range.By changing Pb/Sr ratio, can adjust flexibly Range of measuring temp, increase the Pb of 1mol%, can be by Curie temperature to approximately 7 ℃ of high-temperature mobiles, and increase the Sr of 1mol%, Curie temperature can be moved to approximately 7 ℃ to low temperature.
Advantage of the present invention and beneficial effect: (1) the present invention is between-70 ~ 100 ℃, specific inductive capacity and temperature have good linearity relationship, the accurately variation of indicated temperature, has advantages of that temperature measurement accuracy is high, the linearity good, high conformity and stable and reliable for performance.(2) because material is to adopt ceramic powder sintering to form, there is good corrosion resistivity and stability.(3) adopt the synthetic temperature sensitive ceramic powder of conventional solid-state method or sol-gel process, easy to operation, sintering process is simple, raw material is cheap.
Accompanying drawing explanation
The XRD figure of Fig. 1 embodiment 1 and 2 samples;
The SEM figure of Fig. 2 embodiment 1 and 2 samples;
The family curve that the dielectric constant with temperature of Fig. 3 embodiment 1 and 2 samples changes.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: adopting conventional solid-state method to prepare chemical composition is Pb
0.10sr
0.90tiO
3+ 0.0005Al
2o
3+ 0.003SiO
2the temperature sensitive ceramic powder of+0.037PbO and temperature sensitive stupalith, step is as follows:
(1) press chemical formula Pb
0.10sr
0.90tiO
3take respectively 5.6068g SrCO
3, 3.2986g TiO
2, 1.0151g PbO;
(2) take distilled water as medium ball milling 6-48h, after oven dry, 850 ℃ of calcining insulation 2h, obtain principal crystalline phase powder;
(3) preparation of temperature sensitive pottery
Take respectively 5.0000g principal crystalline phase powder, 0.0025g Al
2o
3, 0.015g SiO
2with 0.185g PbO, add water and form slurry, the agate ball of take carries out ball milling as ball-milling medium, and Ball-milling Time is 6-48h;
The dried sample of ball milling is added to PVA mixing granulation, under 4MPa pressure, be pressed into the disk of 8mm, carry out sintering and be incubated 6h in 1200-1300 ℃, make pottery.The XRD figure of ceramics sample and SEM figure are respectively as shown in 1# in Fig. 1 and Fig. 2, the specific inductive capacity temperature characteristics figure of sample is shown in the 1# in Fig. 3, as seen from Figure 3, prepared material dielectric constant variation with temperature has the good linearity, accurately the variation of indicated temperature.
Preparation consists of: Pb
0.10sr
0.90tiO
3+ 0.0005Al
2o
3+ 0.003SiO
2the ceramic powder of+0.037PbO, adopts once through method in Sol Gel process to prepare powder and temperature sensitive stupalith, and concrete steps are as follows:
(1) take butyl titanate 38.2688g, ethyl orthosilicate 0.2278g, adds 35ml glacial acetic acid, stirs;
(2) weigh the plumbous 6.0741g of acetate trihydrate, strontium acetate 21.8394g, nine water aluminium nitrate 0.0813g, use 90ml deionized water dissolving, and with step (1) solution mix and blend, room temperature reaction 0.5h, obtains light yellow vitreosol;
(3) colloidal sol is stirred to gelation, still aging, in 90 ℃ of dry dry gel powders that obtain;
(4) step (3) gel powder is obtained to temperature sensitive ceramic powder at 800 ℃ of calcining 1h;
(5) by the temperature sensitive ceramic powder of step (4) through granulation, compressing tablet, at 1300 ℃ of sintering 2h, obtain potsherd, apply after silver slurry silver ink firing welding lead and obtain temperature sensitive ceramic component.
In Fig. 1, the XRD figure of 2# can find out, the pottery by 1300 ℃ of sintering is typical perovskite structure, and corresponding SEM figure and the warm curve that is situated between are shown in Fig. 2 and Fig. 3 shown in 2# successively.As seen from Figure 3, the specific inductive capacity of sample and temperature have good linear relationship, well the variation of indicated temperature.
Embodiment 3
Adopt once through method in Sol Gel process to prepare and consist of Pb
0.15sr
0.85tiO
3+ 0.0008Al
2o
3+ 0.004SiO
2the temperature sensitive ceramic powder of+0.065PbO.
Preparation method is similar to Example 2, difference is, step (3) gel powder obtains temperature sensitive ceramic powder at 900 ℃ of calcining 1h, then through granulation, compressing tablet, at 1250 ℃ of sintering 3h, obtain potsherd, apply the rear silver ink firing of silver slurry welding lead and obtain temperature sensitive ceramic component.
Claims (7)
1. general formula Pb
xsr
1-xtiO
3+ aAl
2o
3+ bSiO
2the ceramic powder that+cPbO represents, wherein, x=0.10 ~ 0.20, a=0.0002 ~ 0.001, b=0.001 ~ 0.006, c=0.015 ~ 0.075.
2. the preparation method of ceramic powder described in claim 1, is characterized in that comprising the following steps:
(1) by stoichiometric proportion, butyl titanate and ethyl orthosilicate are dissolved in to glacial acetic acid;
(2) aqueous solution of above-mentioned solution and lead, strontium and aluminum metal salt, stirs and obtains light yellow vitreosol;
(3) colloidal sol is stirred to gel, still aging, in the 70-120 ℃ of dry dry gel powder that obtains;
(4) dry gel powder obtains ceramic powder at 700 ~ 1000 ℃ of calcining 0.5 ~ 2h.
3. the preparation method of ceramic powder according to claim 2, is characterized in that: in step (2), described lead, strontium and aluminum metal salt are nitrate or acetate.
4. the preparation method of ceramic powder described in claim 1, is characterized in that: by stoichiometric proportion, take respectively SrCO
3, TiO
2and PbO, take distilled water as medium ball milling post-drying, 800 ~ 900 ℃ of calcinings obtain principal crystalline phase powder, by stoichiometric proportion by principal crystalline phase powder and Al
2o
3, SiO
2add water with PbO and form slurry, ball milling.
5. a stupalith, is characterized in that: by ceramic powder claimed in claim 1 further through granulation, compressing tablet, 1100 ~ 1350 ℃ of sintering 1 ~ 6 hour.
6. the application of ceramic powder in Temperature Detector described in claim 1.
7. application according to claim 6, is characterized in that: temperature detection scope is-70 ℃ ~ 100 ℃.
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